Triazine monoazo dyestuffs



United States Patent 6) '2 ApplicationNovembertzfi, 1955., lie- 45L177Glaimspriority, application GreatfBritain November; 29, .1954:

Q (g ut-15a);

were P r i ular t r l te to. ne mpn eh y flifi hither? valuable, o heprod ct ve... qlpura ope 2 s q is mat 4 I i nited. K n d m PF? I fii aiao. 209 7 h r l amped t ma ufe tureoiazq yetalls bv ifi ie i q qy st fiawnta in' o e i more wafnnr ql nuc i, (1) x' m ia herr w t other wer copares y Ia 9 whi h ead 1th. he fo mat n" of dye e med rr d st c'en i ig'bn 9! m e vani nuclei; or (2) b unitin a o d est f c nt nin ppree newer insa the t eaeh. ther smot t m-v i x tr i ls Qr s itabl re id e 2vfeaet e l w fla the. a q ot a u al de a s fira ie he e d sea ed 011 1 9dyestutfs, wherein there are attached to two 'chlorinei atomsgand whichare'obtained by react on 0 one molecular proportion of;anarninonaphtholsul-l phonic acid with one molecular proportion cyauuricchloride and subsequently treating fth'e product diazo compound;obtained by diazo'tisingffor" example; aniline, 'ptoluidine', p-aminoacetanilide' 'orf m xylidine. There are also disclosed monoazo dyestuffs,wherein there are -httached to thetriaz ine ring one chlorine atom andone anilino group, andwhichjare 'obt'aine'd by message of-onemolecular-proportion of an aminonaphthol su'l phonic'acid and onemolecular proportionof aniline with one molecular proportion ofcy'anuric chloride and; sub sequently 1 treati'ng the product with adiazo compound obtained for example by diazotising aniline or asubstitution product of aniline having a negative substituent, forexample Cl, CO H or Q H, or m-xylidiue or-a monosulphonatednaphthylamine.

There is no compound disclosed in the said specification, however, whichcontains attached to the triazine ring, in addition to two atoms ofchlorine, the residue of an aminonaphthol sulphonic acid couplingcomponent to which is attached the residue or a diazo component of the."b nzene series whichtcontainssulphonic acidtgroups.

We have found that-certain-monoazodyestufifstof'the kind.entainingtwochlorine atcmsl attached to the-tria zvineyring and also anamin'onaphthol sulphonic acid, radicalcontaining anorthQ-sulphophenylazo substituen't, whi hvdyestutfs intheir freea'cidform' arerepresented; by -the;fo mula:given below have superiortinctorial value and v Superior fastness tonwet treatments, as;-compared With-11191192120 dyestuffs of: comparable shade specificallyak59 i in United Kingdom specification; No. 209,723 containing only Ichlorine atom attached to the tri-' azine ring-andsuperior-fastness tolight ascompared with: 11 0 192110 dyestuffs ofr'comparable. shadespecifically desclibed in UnitedtKingdom specification No; 209,723

st. rease,

2,892,828 Pa ented; ae? 3QJ2 2 jecting the textile materialyto theaction of, an acids binding agent in aqueous medium for; ajs'hort time,of; Order of n .v a w m nu e' d ntageou not r e t? f a c v-t iichlfa l.odiu t v sl birl Sqd m u hai g v. .v o

According "to our invention we provide new -St h n t arm; 9? th, hfq imlf 3E.

wherein the benzene nucleusiA optionally bears further substituents'other than; hydroxyl and amino groups, X stands for a hydrogen atom-'or'a'substituent other than halogen, and R stands for a hydrogen atom orfor a hydrocarbon radical. r According tofour invention we also providea process for the manuf cture of 'th'said'new mqneazo dyestulfiii whichcomprises diazo tising a p im q g g amin'i oftheformulaz' t.

- whfit fl s, the-meaning stat above.

- one molecular proportion'bf 'cyanuric chlqridei which; contain twochlorinezatoms attached tothe 'triazine ring; but which do," not containthe ortho sulphophenylazo' substituent, when: the dyestuffs are.pnliedjoscellulosic textile materials by a process whichcomprisesimpregnating the-saidtextile materials with the :dyestufi inaqueous solution and subsequently. 'sub-.

A cordi g af rt ure' ou in ention we. provide an alternative process forthemanufacture ofithe; said Q W' Q d t c fi wh h qmnr ss eac in amonoazo compound which is in the form o fi its free acid isfof the,formulai NHR h r in X e R ha e e e i s stated. above. nd-Z the benzenenucleus A may optionally bearjfur'ther s stituents other than hydroxyland amino'groups';

methoxyaniline-6-sulphonic acid, 4-methoxyaniline-2-sulphonic acid andS-methoxyaniline-2-sulphonic acid.

As coupling components for use in the azo coupling process of ourinvention there may be used for-example the primary condensationproducts obtained by reaction of 2-amino-S-naphthol-7-sulphonic acid, orderivatives of Z-amino-5-naphthol-7-sulphonic acid containing ahydrocarbon radical as a substituent in the amino group, with onemolecular proportion of cyanuric chloride in aqueous medium.

The monoazo compounds used as starting materials for reaction withcyanuric chloride by the alternative process of our invention may beobtained by diazotising a primary aromatic amine, as defined above, andcoupling the diazo compound thus obtained in alkaline medium with acoupling component of the formula:

Ho s NHR wherein R has the meaning stated above, or alternatively, whenthe said diazo compound does not contain an acylamino group, by couplingthe said diazo compound in alkaline medium with the N-acyl derivative ofsuch a' coupling component and subsequently;removing the acyl group byhydrolysis with for example caustic soda.

In the process of our invention, the diazotising of the amino compoundand the coupling of the diazo compound thus produced with the couplingcomponent is preferably carried out at a temperature below 5 C.,conveniently at -5 C. In the process of our invention wherein there isused a coupling component containing the cyanuric nucleusit isadvantageous to use for the coupling reaction the said couplingcomponent prepared in situ at temperatures of 05 C. by methods knownfrom the literature and to carry out the couplings at similartemperatures and at as low a pH as is possible for efficient coupling,in order that side reactions, for example hydrolysis of the chlorineatoms remaining attached to the triazine ring, are minimised.

Similarly, in order to avoid such side-reactions during manufacture andstorage it is generally preferable to isolate the new dyestuffs from themedia in which they have been formed at a pH from 6.4 to 7.8 and to drythe resultant dyestufi pastes at relatively low temperatures, forexample between 20 and 40 C., preferably in the presence of bufferingagents suitable for maintaining a pH value of about 6.5. Examples ofsuch bufiering agents are mixtures of disodium hydrogen phos phate andsodium dihydrogen phosphate or of disodium hydrogen phosphate andpotassium dihydrogen phosphate. In the manufacture of the new dyestuffsof the inven tion by the said alternative process namely by reactingequimolecular proportions of a monoazo compound of the formula statedand cyanuric chloride the reaction is preferably carried out in aqueousmedium at temperatures between 0 and C. e r

The new dyestuffs of this invention in the form of their alkali metalsalts are readily soluble in water and areespecially suitable for theproduction of level and fast orange colourationson cellulosic textilematerials by continuous dyeing techniques, for example by a processwhich comprises impregnating the said textile materials with a solutionof the dyestuif and thereafter subjecting the textile materials,optionally after drying, to the action of an acidbindingagent forexample caustic ,soda, in aqueous medium which advantageously containsan elec troly'te' such as sodium chloride or sodium sulphate, for ashort period of time, commonly of the order of only a. few minutes, attemperatures conveniently lying between v,

atmospheric temperature and the temperature of the boil- 1ng s 0lution,and also by printing methods, for example bya which comprises applyingto the said textile materials a printing paste containing the dyestufiand substance on heating or steaming liberates an acid-binding agent,for example sodium bicarbonate, and subsequently subjecting them to theaction of heat or steam. The colourations thus producedTpossss a verygood fastness to light and a high degree of fastness to wet treatments,especially to repeated washing.

Y The invention is illustrated but not limited by the following exampleinwhich the parts are by weight:

Example 1 A solution of 18.5 parts of cyanuric chloride in 100 parts ofacetone is poured into a stirred mixture of 400 parts of water and 400parts of crushed ice, and 2 parts of 2 N hydrochloric acid are added. YTo the suspension of cyanuric chloride thus obtained there are addedduring 40 minutes, and at a temperature below 5 C., 26.1 parts of thesodium salt of .2-amino-5-naphthol-7-sulphonic acid as a solution in 480parts of water, made faintly alkaline to Brilliant Yellow by theaddition of sodium carbonate. The mixture is stirred at a temperaturebelow 5 C. for 1 hour and then 6 parts of 2 N sodium carbonate solutionare added and stirring is continued at the same temperature for another20 minutes. A suspension of the diazo compound from 16.45 parts ofaniline-2- sulphonic acid, obtained by diazotising the aniline-2-sulphonic acid in a mixture of 200 parts of water and 18 parts ofhydrochloric acid (specific gravity 1.18) at a temperature between 0 and2 C. with 6.55 parts of sodium nitrite, is then added to the mixtureduring 5 minutes at a temperature between 0 and 4 C. 40 parts of sodiumacetate crystals are added during 10 minutes and the mixture-is stirredat 0 to 4 C. for 90 minutes,

- after which time sufficient anhydrous sodium carbonate is graduallyadded during a further 90 minutes to render the aqueous medium slightlyalkaline to litmus. Suflicient sodium chloride to give a concentrationof 200 grams per litre is added and the mixture is stirred for 30minutes, while the temperature is maintained between 0 and 4 C., and themixture is filtered, and the solid on the filter is washed with 20%brine and then with acetone and dried at 20 to C. The product'forms ared-brown solid'which dissolves in water to give an orange solution andin concentrated sulphuric acid to give a bluish red solution. 7

This product in the form of its free acid has the formula: I

An alternative method for the preparation of the dyestulf described inExample 1 is as follows:

185' parts 'of cyanuric chloride are dissolved in 100 parts of-dryacetone'andthe solution is added graduallywith stirring to a mixture of300 parts of water and 400 partsof crushed ice. To the stirredsuspension of cyanuric'chlor'ide so formed there is added during 40fying the product to remove from it any dyestuff formed by couplingon'the 8-position of the N-acetyl 2-amino -5- naphthol-7-sulphonic acid,and hydrolysing to remove the acetyl group by heating-it in an aqueoussolution containing about 4% caustic soda at 85' C.

The temperatureof' the. reaction mixture is maintained between=0?z and 42C. ;and,within afew minutes of com plet gjthe addition. of aminoazocompoundnone of it.

{mains unchanged. The. ac'idsolutioniformed is made neutral to litinusby the additionof sodium carbonate solution and there is also added toit a solution containing 7 parts of anhydrous disodium liydrogenphosphate and 125 parts of anhydrous potassium dihydrogen phos-Sufiicient salt to give a concentration of lQQgrams-per litre is. added,and the mixture is stirred'lifor a short time and is then filtered. Thesolid is mix'edintirhately"with'422 arts of anhydrous disodium hydrogenphosphate and 7.5 parts of anhydrous potassium dihydrogen phosphate anddried at 20-30" C If the aminoazo compound used for condensation withcyanuric chloride in this example is replaced by an equivalent amount ofone of the aminoazo compounds named in the list below and prepared ineach case by coupling a diazo compound obtained from a derivative ofaniline- 2-sulphonic acid with an N-acyl-2-amino-5-naphthol-7- sulphonicacid, for example N-acetyl-2-amino-5-naphthol- 7-sulphonic acid or anN-acyl-N-substituted Z-amino-S- naphthol-7-sulphonic acid, for exampleN-acetyl-N-methyl-2-arnino-5-naphthol-7-sulphonic acid and removing ifnecessary any product formed by coupling on the 8- position of theZ-amino-5-naphthol-7-sulphonic acid residue and then hydrolysing thepurified 6-coupled product by heating with caustic soda in aqueoussolution, then the alternate dyestuffs formed all have the capability ofgiving bright colourations on cellulosic materials for example cotton,when applied irom aqueous solutions by padding and after-treating thepadded material, optionally after drying with an aqueous solutioncontaining caustic soda and sodium chloride. The colourations soobtained, the shades of which given by the products from the variousaminoazo compounds are also listed below all show very good fastness tosevere washing and to phate in "160' parts of" water.

amazes soda boiling.

Aminoazo compound reacted with eyanuric Shade of dyeings chloride oncotton 4-Toluidine-3-sulphonie acid diazotised and coupled Brightreddish with Z-amino5-naphthol-7-sulphonic acid. orange.5-ehloro+methyl-2-aminobenzene-sulphonic acid Orange.

diazotised and coupled with 2-amino-5-naphthol- 7-sulphonic acid.4-chloroaniline-2-sulphonic acid diazotised and Do.

cou led with 2-amino-b-naphtholJ-sulphonlc Aniline-2:5-disulphonic aciddiazotised and coupled with 2-amino-5naphthol-7-sulphonic acid.

Aniline-Z-sulphonic acid diazotised and coupled withN-methyl-2-amlno-5-naphthol-7-sulphonic acid.4-chloro-5-methyl-2-arninobenzenesulphonic acid dlazotised and coupledwith 2amino5-naphth0i- 7-sulphonie acid.

a-aminoanlsolei-sulphonic acid diazotised and con led with2-arnino-5-naphthol-7-sulphonic ac 3-toluldine-4-sulphonic aciddiazotised and coupled with 2-amino-5-naphthol-7-sulphonie acid.

Golden orange.

Reddish orange.

Orange.

Yellowish orange.

What I claim is:

l. Monoazo dyestufifs which, in the form of their free acids, are of theformula:

bearing an -S0 H group.

son: on o s oin on n CH, ON=N N N Hols -NH-(: l-Cl soar on I1 01 N= on.11038 NHgl (3-01 son; 0H 01 c1 N=N N Hols NHC o-ci sc n on 01 5 GM H038H038 NH- x-c1 SOaH on or 0' N=N on, N \N noas I i("3 c-ci sons 0H :1CH;QN= m N N 01 Hots -NH- (J-Cl 011,0 on or 5 Q N N 0,11 Hots NH- d-oisonar on or 011, Ross -NH-il i-C1 (References on following page)kelerences Cited in the file of this patent UNITED STATES PATENTS'Fritsche et a1. Apr. 24, 1928 Hofia et a1. Apr. 21, 1931 Haller et a1.Nov. 8, 1932 Bush May 7, 1935 Dove Sept. 21, 1937 Blackshaw et a1. Jan.18, 1944 8 2,384,283 Conrad et al. Sept. 4, 1945 2,722,527 Wahrli et a1.NOV. 1, 1955 FOREIGN PATENTS 111,274 Switzerland Aug. 1, 1925

1. MONOAZO DYESTUFFS WHICH, IN THE FORM OF THEIR FREE ACIDS, ARE OF THEFORMULA: